j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456

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Residual stress during heat treatment of steel grinding balls
C. Camurri
a
, C. Carrasco
a,
, J. Dille
b
a
Universidad de Concepci on, Department of Materials Engineering, Casilla 53-C, Concepci on, Chile
b
Universit e Libre de Bruxelles, Facult e des Sciences appliqu ees/ ecole polytechnique, Avenue F. Roosvelt 50CP194/03, Brussels, Belgium
a r t i c l e i n f o
Article history:
Received 24 April 2007
Received in revised form
25 October 2007
Accepted 8 January 2008
Keywords:
Grinding balls
Heat treatment
Martensite
Residual stress
a b s t r a c t
This work aimed to model the temperature distribution, phase transformation and resid-
ual stress induced during the heat treatment of grinding balls of 3 and 5in. diameter. The
temperature model considered factors such as the heating of the water and the formation
of a steam layer that surrounds the balls at the start of the quenching. The model of the
residual stress eld considered: the temperature distribution, the force equilibrium equa-
tions and the constitutive thermo-elastic relationships, including the expansion due to the
austenitemartensite transformation.
A good agreement between the experimental and theoretical values for the temperature
distribution was obtained with the differences at the end of the quenching being no higher
than 0.5%. The experimental behavior of the balls in a mill simulator, as well as the residual
stress measured by X-ray diffraction, agreed satisfactorily with the theoretical predictions.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Moly-Cop at Talcahuano, Chile, produces steel grinding balls
mainly of 3 and 5in. (7.62 and 14.70cm, respectively) diameter,
using rolling or forging processes (see Table 1 for details of
their composition).
Immediately after the metal working the balls, at 800

C,
were quenched in water at an entry temperature of 50

C and
for 80 and 180s for the 3 and 5in. diameter 2R of the balls,
respectively. After quenching, the balls were cooled in air for
temperature homogenization for 40 and 120s, respectively, a
process known as equalization. The 3in. diameter balls were
then stored in boxes in order to allow them to slowly reach
ambient temperature. When the 5in. diameter balls had been
equalized a four-step annealing process, each step lasting for
1h, was performed: cooling in the furnace by air pressure,
then heating the balls to 230

C by hot air, then slow cooling

down to 220

C, and nally cooling from 220

C to the ambient
temperature.

Corresponding author. Tel.: +56 41 2207170; fax: +56 41 2203391.

E-mail address: ccarrascoc@udec.cl (C. Carrasco).
During the heat treatment, and as a result of the ther-
mal and structural gradients, residual stresses are generated
which can jeopardize the working life of the balls and, in
some cases, cause fracture before they are used. The aim of
this work was to model and resolves in an analytical way
the residual stress eld induced during the quenching and
equalization of the steel balls and thus determine their possi-
ble cracking or fracture points. Also, and for further works,
the model can be useful for predict the optimal operating
conditions during quenching, for instance, the initial temper-
ature and ow of the water, in order to reduce the residual
stresses.
The work was carried out in two main stages: rst, the
radial distribution of the temperature of the balls during the
quenching and equalization processes was modeled using
the explicit nite difference method and validated experi-
mentally. Also, the radial distribution of the martensite was
calculated. Second, the residual stress eld was simulated
using the data obtained in the previous stage.
0924-0136/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2008.01.007
j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456 451
Nomenclature
C
p
caloric capacity
E elasticity modulus of the mix
austenitemartensite
h heat transfer coefcient ball ambient
h
convective
convective heat transfer
h
radiant
radiant heat transfer
K thermal conductivity
M
s
temperature of beginning of martensitic trans-
formation
R radius of the balls
r radial coordinate
r
a
radius of a sphere of 1g of austenite used as
reference for calculus
r
ma
radius of a sphere of 1g of the mix
austenitemartensite
T radial temperature of the balls.
T
s
surface temperature of the balls
T
am
ambient (steam, water, air) temperature
u radial displacement
Greek letters
thermal lineal expansion coefcient
lineal expansion coefcient due to phase trans-
formation

rr
,

radial and circumferential strain, respectively

v Poisson modulus
,
i
density of i phase (i =a, austenite; i =m,
martensite)
o
rr
, o

, o
ef
, o
0
, o
R
radial, circumferential, effective or
equivalent, yield and rupture stress, respec-
tively
LM volumetric fraction of martensite (or annealed
martensite)
2. Models
The thermal and residual stress models are as follows.
2.1. Temperature distribution of the balls
For modeling the radial temperature of the balls T, the follow-
ing assumptions were made (Camurri et al., 1997; Kreith, 1973;
Incropera and Dewit, 1999; Mills, 1995; Welty, 1979; Farlow,
1982):
The balls are completely spherical and homogeneous, i.e.,
they only have radial temperature gradients.
Fig. 1 Micrography of the center zone of a 5in. diameter
ball.
The heat losses by radiation and the heats of reaction of the
phases formed during the process are neglected.
The thermal conductivity K and caloric capacity of the
steel C
p
depends linearly on the temperature. Addition-
ally, the densities of the only two possible phases presents
(see Fig. 1), austenite and or martensite, were assumed as
8.03g/cm
3
and 7.75gr/cm
3
, respectively (Totten et al., 1992).
The heat losses from the water used for quenching are neg-
ligible.
With this assumption, the heat equation to resolve is
K

2
T
R
2

+
2
r
T
R
= ,

t
(TC
p
) (1)
With the following border conditions
T
r
(0. t) = 0 and K
T
r
(R. t) = n(T
s
T
am
)
where h is the coefcient of heat transfer between the surface
of the ball at T=T
s
and the media at T=T
am
.
In a previous work (Camurri et al., 2003; Garca, 2000), the
temperature of the quenching water was assumed to be con-
stant and the vapor layer formed around the balls at the
beginning of the process was neglected. These hypotheses
yielded a poor correlation between theory and experience, so
both effects were included in the present model.
Hence, in a rst cooling stage during the quenching, until
the surface temperature Ts of the balls is around 220

C, a
radiation and convection heat transfer mechanism across the
vapor layer surrounding the balls is considered. In this case,
T
am
=100

C and h=h
convective
+0.75h
radiant
. The formula for
determines the coefcient h
convective
as a function of the tem-
Table 1 Composition (wt.%) of the steel of 3 and 5in. diameter balls
Diameter C Mn P S Si Cr Mo Al Ti Nb V Cu Ni
3 1.13 0.93 0.01 0.01 0.23 0.76 0.05 0.02 <0.01 <0.01 <0.01 0.2 0.05
5 0.74 0.94 0.01 0.02 0.21 0.80 0.01 <0.01 0.02 0.04 0.01 0.06 0.05
452 j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456
perature can be found in Incropera and Dewit (1999). This
formula involves the ball diameter and physics and thermal
properties of the liquid and vapor water such as density, ther-
mal conductivity and cinematic viscosity; also the formula
has a constant which depend of the geometry of the bodies,
in this case 0.67 for spheres. For the radiation coefcient an
emissivity of the steel of 0.9 was supposed.
In the second cooling stage during the quenching, until
T
s
105

C, the cooling of the balls is produced by vapor

transport from its surface, and the temperature is considered
as T
am
=100

C. In this stage the coefcient h can be found

in Incropera and Dewit (1999) and depends of the thermo-
physics properties of saturated liquid and/or vapor such as
density, specic heat, cinematic viscosity and supercial ten-
sion. There are also two constant, C and n, in the formula
for obtain h. These constants are related with the system
surface-uid, and the values for the studied steelwater are
0.013 for C and 1.0 for n (Incropera and Dewit, 1999). Finally,
the third cooling stage begins when the surfaces of the balls
reachthe boiling temperature of the water, and the heat trans-
fer mechanism is pure convection. In this case T
am
is equal to
the instantaneous temperature of the water, which is calcu-
lated by main of a heat balance among the heat loosed for
the ball and transfer to the water, with initial temperature of
50

C.
During the equalization and annealing, the heat losses
from the surface of the balls to the air are only by convec-
tion. In all cases, h is function of the surface temperature of
the balls.
Eq. (1) was solved by the explicit nite difference method,
using algorithms for the internal, central and supercial
nodes. Performing with the stability conditions, in the case
of 3in. diameter balls, the radial increments were R/20 and
the temporal increments were 0.02s and 0.05s in quenching
and equalization, respectively. For 5in. diameter balls, those
increments were R/40, 0.05s in quenching and 0.025 in both
equalizationandannealing. The temperature distributionwas
validated by inserting thermocouples in three different posi-
tions in the balls: the center, R/2 and R0.7mm, where R is
the radius of the balls. Additionally, the temperature of the
quenching water was continuously measured during the pro-
cess in order to compare it with the model results.
2.2. Residual stress of the balls
To model the residual stress eld, the following hypotheses
were made:
Throughout the cooling there are only two phases in the
balls: austenite and/or martensite, as Fig. 1 shows.
The induced residual stresses are only normal stresses.
The residual stresses induced in the austenite are negligible
due to the low yield stress of this phase at a temperature
above M
s
, the temperature at which start the martensitic
transformation. For example, at 400 and 600

C the yield
stress of austenite is 120 and 80MPa, respectively, while the
yield stress of martensite at 200

C is 800MPa (Okamura and

Kawashima, 1988).
In general, the modeling of coupled thermo mechanical
problems with also phases transformations normally use
numerical techniques such as nite elements for its resolu-
tion. For example, in Hossain et al. (2004), this methodology
is addressed in the modeling with a posterior experimental
validation by means of neutrons diffraction, of the resid-
ual stresses induced during the quenching of stainless steel
spheres of 30mmdiameter. In the present work, a simple ana-
lytical solution for the residual stresses eld in grinding balls
is presented based on the following equations.
2.2.1. Equation of Equilibrium of radial forces
o
rr
r
+2
(o
rr
o

)
r
= 0 (2)
where o
rr
and o

are the normal, radial and circumferential

stresses, respectively.
2.2.2. Equations relating deformations and displacements

rr
=
u
r
and

=
u
r
(3)
where u,
rr
and

are the radial displacements, and the radial

and circumferential strain, respectively.
2.2.3. Constitutive thermo-elastic-phase transformation
equations
These include the thermal expansion coefcient of the
steel and the linear coefcient of expansion due to the
austenitemartensite phase transformation.

rr
=
(o
rr
2vo

)
E
+F(r) and

=
(1 v)
E
o

v
E
o
rr
+F(r)
(4)
and
F(r) = LT(r) + LM(r)
where E and v are the elasticity and Poisson modulus,
respectively of the austenitemartensite mix at temperatures
below M
s
, obtained from reference data for their individual
modulus (Okamura and Kawashima, 1988) and, in the case of
the Youngs modulus E, were also obtained experimentally in
this research fromtensile curves of standard samples of 5mm
in diameter and 25mm gage length L
0
. These samples were
quenched at temperatures below M
s
and subjected to tensile
tests by an Instron machine at those temperatures. The slope
of the linear part of the stressstrain curve corresponded to
the E values (Rodrguez, 2006).
The symbol corresponds to the thermal expansion coef-
cient of this mix, corresponds to the linear expansion
coefcient due to the phase transformation from austenite to
martensite during quenching and equalization or the linear
contraction coefcient due to the phase transformation from
martensite to annealed martensite during the annealing of
5in. diameter balls. Finally, LT(r) and LM(r) are the changes
in the temperature and the volumetric fraction of marten-
site formed at each radial position for temperatures below
fromM
s
, respectively. Determinedthe temperature of the balls
for each time and knowing the CCT curves of the steels for
obtain M
s
, it is possible determines the volumetric fraction
j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456 453
of martensite formed (LM(r)) using the KoistinenMarrburger
equation (Krauss, 1990). Obviously, LM=0 if the temperature
in some radial portion is higher than M
s
. As the densities of
the austenite (,
a
) and the martensite (,
m
) are known as well
as the fraction of formed martensite LM(r), the coefcient (r)
is determined as
=
r
ma
r
a
r
a
(5)
where r
ma
and r
a
are the radius of the 1g of spherical shape
(base of the calculus) of the mix austenitemartensite or only
austenita, respectively, and which are calculated as
r
a
=

3
4,
a
and r
ma
=

3
4(1 LM),
a
+LM,
m
)
(6)
If must be calculated in the transformation martensite
to annealing martensite, the procedure is analogous, and in
this case LM represents the fraction of annealing martensite
and should be determined from an annealing parameter as is
shown in Shi et al. (2001).
By combining formulas (2)(4), the radial equation of the
force equilibrium can be expressed in terms of the radial dis-
placement u as

1
r
2

r
(r
2
u)

=
1 +v
1 v
F(r)
r
(7)
Note that F(r) is known because the radial distribution of tem-
perature T and the coefcient (r) have been determined as
was described previously.
Then by a double integration the radial displacement u is
obtained
u(r) =
(1 +v)

r
2
F(r)dr
r
2
(1 v)
+C
1
r
3
+
C
2
r
2
(8)
Using the constitutive thermo-elastic-phase transforma-
tion Eq. (4), nding the stresses in terms of the strains
expressed as a function of u and u/r, the radial normal stress
is
o
rr
=
E
(1 +v)(1 v)

(1 v)
u
r
+2v
u
r
(1 +v)F(r)

(9)
where C
1
and C
2
are constants which must be determined
from the following border conditions
If r =R (radius of the ball), o
rr
=0.
If T(r =0) <M
s
, then o
rr
/r =0.
If T(r =0) M
s
, then o
rr
(r r*) =0, where r* is the radius for
which T(r =r*) =M
s
.
Additionally, if for some radius r** the effective or equiva-
lent stress o
ef
dened in this case as o
ef
=|o
rr
o

|, with o

the circumferential stress, results equal or greater than the

yield stress of the steel o
0
, then o
ef(r=r**)
=o
0
, if o
ef
<o
R
(rup-
ture stress), or o
ef(r=r**)
=0 if o
ef

R
. Due to the low ductility
of the steel of the balls, their rupture stress is closely equal
to their tensile strength. Once the radial distribution of the
radial residual stress has beenobtained, the radial distribution
of circumferential stress is obtained directly from the equi-
librium Eq. (2). More details of the mathematical models are
Fig. 2 Temperature distribution during quenching of 3in.
diameter balls.
given elsewhere (Camurri et al., 2003; Garca, 2000; Rodrguez,
2007).
3. Results and discussion
Figs. 2 and 3 showthe experimental and theoretical results for
the radial distribution of temperature for 3in. diameter balls
during quenching and equalization, respectively.
Good agreement betweenthe present model and the exper-
imental data is observed. In the other hand, a poor correlation
was obtained in the stage of quenching if the thermal model
not included the effect of the initial formation of vapor layer
surrounding the balls (Camurri et al., 2003; Garca, 2000) which
cause a higher cooling rate in the surface of grinding balls.
Fig. 4 compares the experimental and theoretical values
for the temperature of the quenching water during the same
process.
There was good agreement between the experimental
water temperatures during quenching. They were slightly
lower than the theoretical temperatures at the end of the pro-
cess because the heat losses to the ambient were neglected.
Fig. 3 Temperature distribution during equalization of
3in. diameter balls.
454 j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456
Fig. 4 Experimentaltheoretical comparison of quenching
water temperatures.
Fig. 5 shows the numerical radial distribution of martensite
in 3in. diameter balls at the end of quenching and equaliza-
tion.
Fig. 5(a) indicates that at the end of quenching and for a
radius smaller than 1.9cm, the temperature of the balls was
higher than M
s
(M
s
=220

C for the steel used), and conse-

quently nomartensite was observedinthat zone. This implies,
according to the previous discussion, that the residual stresses
at that radius are negligible.
Figs. 3 show that at the end of the equalization the centers
of the balls have a temperature closely of 150

C, whichimplies
that at that moment there is 54% of martensite when r =0. As
a result, when the equalization concludes, all the balls have
residual stress.
Fig. 6 shows the modulus of elasticity as a function of the
temperature of the austenitemartensite mix obtained from
the reference data(OkamuraandKawashima, 1988) andexper-
imentally in this investigation (Rodrguez, 2006).
Fig. 6 shows a very good agreement between both data
groups up to temperatures of around 170

C. For higher
temperatures, the experimental data obtainedfromthis inves-
tigation are lower than the data from the literature for
martensite alone. This is probably due to the expansion effect
of the pull roads used to subject the sample during the test,
which implies a longer displacement for each tensile strength.
Since a temperature extensometer was not available, the elon-
gationof the sample was obtainedfromthe displacement data
recorded by the Instron machine minus the effect of the elon-
gation of the equipment, including the pull roads, which was
determined from previous traction tests at room temperature
made on steel samples of known modulus of elasticity.
Figs. 7 and 8 show the theoretical radial distribution of
circumferential stress for balls of 3 and 5in. diameter, respec-
tively, at the end of the quenching and equalization. Some
experimental measurements of residual stresses on the sur-
face of industrial 3 and 5in. balls, i.e., after the slow cooling
in boxes after the equalization (3in. diameter balls) or after
annealing (5in. diameter balls) are included. These values
were obtained by X-ray diffraction (XRD) with a diffrac-
Fig. 5 Numerical martensite distribution in balls of 3in.
diameter: (a) at the end of the quenching and (b) at the end
of the equalization.
Fig. 6 Variation in modulus of elasticity with temperature
of the austenitemartensite mix. Comparison between
reference and experimental data.
j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456 455
Fig. 7 Theoretical radial distribution of circumferential
stress for 3in. diameter balls at the end of quenching
(dotted line) and equalization (continuous line) and
experimental (spots in black).
tometer (Siemens D 500). Also, as a reference, in depth
experimental values of the residual stresses were obtained
by measures on 1.0cm1.0cm6.5cm parallelepipeds cut
fromthe 3in. diameter balls, or from1.0cm1.0cm12.0cm
parallelepipeds from the 5in. diameter balls.
Note from Figs. 7 and 8 that after the quenching, in zones
where there are only austenite, the residual stresses are cero,
while after the equalization, the totality of the ball as the mix
austenitemartensite and, as a consequence, all the mate-
rial has residual stresses. In the other hand, it is observed
that the absolute values of the residual stresses induced dur-
ing the quenching, are greater than the induced during the
equalization, just because that treatment has the function of
Fig. 8 Theoretical radial distribution of circumferential
stress for 5in. diameter balls at the end of quenching
(dotted line) and equalization (continuous line) and
experimental (spots in black).
Fig. 9 In time distribution of circumferential stress for 3in.
diameter balls at 0.07mm below the surface at the end of
quenching (dotted line) and equalization (continuous line).
homogenizer the temperature of the balls. It is also interest-
ing to note that the part of the ball with traction stress at the
end of the equalization coincide with the volume with mix
austenitemartensite during the quenching. The circumferen-
tial stresses in this volume at the end of the equalization are
positive because the transformedmartensite during this treat-
ment has less rigidity than the martensite formed during the
quenching, and for this reason the central zones of the balls
have more trends to expand circumferentially. Additionally,
Figs. 7 and 8 show the good agreement between the experi-
mental and theoretical results at the end of equalization of
the circumferential residual stresses on the surface. Also, that
those greater tensile values occur at a certain depth below the
surface of the balls, which coincides with the position of their
fracture when occurs during the heat treatment. The values
of the residual stresses inside the balls show an acceptable
agreement between the theoretical (end of equalization) and
experimental values, the latter being only a reference due to
the effect of cutting the samples from the balls for the XRD
measurements, which introduces distortions and also stress
release.
Fig. 9 shows the time evolution of the circumferential
stress of 3in. diameter ball at 0.07mm below the surface after
quenching and equalization. From that gure can be seen the
variation from compressive stresses at the end of the quench-
ing to traction stresses at the end of the equalization.
4. Conclusions
This simple model of the heat transfer gives the temperature
distribution of the balls during quenching and equalization,
with good experimental agreement.
The model of the residual stresses duly predicts the
observed experimental fact in a mill simulator that, when the
balls fracture during the equalization, the fracture begins at a
certain depth from the surface.
The modeled and experimental residual stresses in the
balls compare well. It should be noted that the experimen-
456 j ournal of materi als processi ng technology 2 0 8 ( 2 0 0 8 ) 450456
tal values measured inside the balls are only intended as a
reference, due to the effects of distortion and stress release
when cutting the samples for the XRD measurements.
Future improvement to the model can be making, such to
include the release of residual stresses in the balls due to plas-
tic micro-deformations during their heat treatment and the
local deformation hardening associated to this phenomena.
Finally, to use the model as a predictor of the better oper-
ational conditions during the heat treatment, such as initial
temperature and ow and agitation of water for reduce resid-
ual stresses of the balls, mayor accuracy in the in depth values
of the residual stresses must be obtained. For this, techniques
such as hole drilling or neutrons diffraction must be used.
Acknowledgements
This work has been supported by The National Council
of Research in Science and Technology of Chile, CONI-
CYT (FONDECYT project no. 1050078). The authors gratefully
acknowledge this support.
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